CN111484041B - Method for preparing lithium hydroxide by using low-concentration lithium-containing solution - Google Patents
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- CN111484041B CN111484041B CN202010305470.4A CN202010305470A CN111484041B CN 111484041 B CN111484041 B CN 111484041B CN 202010305470 A CN202010305470 A CN 202010305470A CN 111484041 B CN111484041 B CN 111484041B
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Abstract
The invention discloses a method for preparing lithium hydroxide by using low-concentration lithium-containing solution, which comprises the steps of dissolving, low-temperature treating and crosslinking a gelling agent and sodium hydroxide and/or potassium hydroxide to obtain a gel ball, then realizing lithium adsorption enrichment and conversion in the low-concentration lithium-containing solution by using the gel ball, and calcining the gel ball adsorbing lithium ions to obtain a lithium hydroxide product; the method realizes the direct preparation of lithium hydroxide products from low-concentration lithium-containing solution, has high lithium recovery rate, does not need a high-temperature concentration and crystallization process and a precipitation process without heating compared with the traditional method, simplifies the process, shortens the process time, reduces the energy consumption and greatly improves the preparation efficiency of the lithium hydroxide.
Description
Technical Field
The invention relates to a method for preparing lithium hydroxide, in particular to a method for preparing lithium hydroxide by using a low-concentration lithium-containing solution, belonging to the technical field of comprehensive utilization of salt lake lithium resources.
Background
Lithium is the lightest alkali metal element, has very active chemical property, has larger abundance in nature, and has the content of about 0.0065 percent in the earth crust. Lithium is also widely used, and relates to the fields of batteries, ceramics, glass, lubricants, refrigerating fluids, nuclear industry, photoelectricity and the like. With the increasing prominence of global resources and environmental problems, lithium is one of the important materials of green energy in the new century, and the development and application of lithium are widely concerned. Lithium exists in nature mainly in two forms, solid ore and liquid ore. The solid ore comprises spodumene, lepidolite, petalite, praalite and the like; the liquid ore mainly comprises salt lake brine, underground brine and seawater. The salt lake lithium resource accounts for 69% of the global lithium reserve and 87% of the global lithium reserve basis, and is an important lithium resource. China has the second lithium resource reserve in the world, second to Bolivian, and the brine contains 79% of lithium resources. The prospect reserves of the brine of the Qinghai and Tibet salt lakes are equivalent to the reserves already proved by other countries, and are one of the most important lithium resources in the world.
Lithium hydroxide is an important basic lithium salt product. The lithium-based lubricating grease prepared from the lithium hydroxide has the advantages of long service life, oxidation resistance, high-temperature stability and the like; as an additive of the alkaline storage battery, the lithium hydroxide can increase the storage capacity and prolong the service life of the battery. In addition, as the only lithium source of the high-nickel cathode material, the lithium hydroxide has greater advantages in sintering temperature and product performance than battery-grade lithium carbonate, and has very wide market prospect in the future.
Throughout the country and abroad, the technological method for extracting lithium salt from salt lake brine mainly comprises a precipitation method, an extraction method, an ion exchange adsorption method, a carbonization method, a calcination leaching method, a schwann method, an electrodialysis method and the like. The preparation method of the lithium hydroxide mainly comprises a lithium carbonate causticizing method, a lithium sulfate causticizing method, a limestone roasting method, a pure alkali water hot-dipping method, a lithium chloride electrolysis method, a lithium sulfate electrolysis method and the like. Lithium carbonate causticizing method, lithium sulfate causticizing method, limestone roasting method and pure alkaline water hot-dipping method are all used for producing lithium hydroxide by using lithium-containing ores. The lithium carbonate causticization method is one of the mainstream processes for producing lithium hydroxide abroad at present, and the method has the advantages of mature process, short production flow, low energy consumption, small material flux and the like, but has higher requirement on the purity of raw materials, complicated impurity removal process and low recovery rate. The lithium sulfate causticization method is the most mature production process for producing lithium hydroxide by spodumene in China. The membrane electrolysis method is mostly adopted for extracting lithium from salt lake brine, but the service life of the membrane is limited, and certain adverse effect is caused to the preparation of lithium hydroxide by the membrane electrolysis method. At present, most of the lithium hydroxide preparation needs to obtain a lithium hydroxide mother solution first, and then perform concentration crystallization to prepare a lithium hydroxide monohydrate product. The traditional method has complex process flow and high energy consumption, so that the process flow of simple development, small environmental pollution and low energy consumption is developed to realize the preparation of lithium hydroxide from low-concentration lithium-containing brine, which is an urgent problem to be solved.
Disclosure of Invention
Aiming at the defects of complex process flow, high energy consumption and the like caused by the fact that the process of concentration and crystallization is needed in the process of preparing lithium hydroxide by the traditional process, the invention aims to provide the method for preparing the lithium hydroxide by utilizing the low-concentration lithium-containing solution.
In order to achieve the above technical objects, the present invention provides a method for preparing lithium hydroxide using a low concentration lithium-containing solution, comprising the steps of:
1) dissolving a gelling agent and sodium hydroxide and/or potassium hydroxide in water to obtain a mixed solution;
2) dropwise adding the mixed solution into liquid nitrogen to form a rubber ball I;
3) carrying out chemical crosslinking reaction on the obtained rubber ball I through a crosslinking agent to obtain a rubber ball II;
4) placing the rubber ball II in a low-concentration lithium-containing solution for adsorption and precipitating lithium ions for adsorption to obtain a rubber ball III;
5) and calcining the rubber ball III to obtain a lithium hydroxide product.
The technical scheme of the invention adopts a rubber ball adsorption method to directly utilize the low-concentration lithium-containing solution to obtain a lithium hydroxide product, and utilizes the rubber balls containing sodium hydroxide (or potassium hydroxide) to realize the adsorption enrichment and the conversion of lithium in the low-concentration lithium-containing solution into precipitates, and the rubber balls after lithium adsorption are easy to naturally settle, thereby greatly improving the solid-liquid separation efficiency, simplifying the process and shortening the process time. Compared with the traditional lithium hydroxide mother liquor concentration and crystallization process, the process does not need the processes of concentration and crystallization, heating and precipitation and the like, and the gel balls after lithium adsorption are easy to naturally settle, thereby greatly improving the solid-liquid separation efficiency, simplifying the process, shortening the process time and reducing the energy consumption.
As a preferred scheme, the glue comprises at least one of gelatin, xanthan gum, dextran gel, polyacrylamide gel and guar gum. Preferred gelling agents readily form gels at low temperatures, have colloidal shapes, have better adsorption of lithium ions, and are readily volatilized or lost at higher temperatures, and therefore, these materials are selected to produce gel spheres, which facilitate recovery of lithium ions.
As a preferable scheme, the mass ratio of the gelling agent to the sodium hydroxide and/or potassium hydroxide is 1: 1-15: 1; in a more preferable scheme, the mass ratio of the gelling agent to the sodium hydroxide and/or potassium hydroxide is 2: 1-6: 1.
Preferably, the mass percentage concentration of the gelling agent in the mixed solution is 3-10%. The concentration of the gelling agent cannot be too high, otherwise the formed mixed solution has high viscosity and poor fluidity, and cannot be easily added into liquid nitrogen, and if the concentration is too low, a stable gel cannot be formed to realize encapsulation and encapsulation of sodium hydroxide (or potassium hydroxide).
Preferably, the amount of the sodium hydroxide and/or the potassium hydroxide is 1 to 5 times of the theoretical molar amount of the sodium hydroxide and/or the potassium hydroxide required for converting all lithium ions in the low-concentration lithium-containing solution into lithium hydroxide. In a more preferable scheme, the dosage of the sodium hydroxide and/or the potassium hydroxide is 2-3 times of the theoretical molar quantity of the sodium hydroxide and/or the potassium hydroxide required by completely converting lithium ions in the low-concentration lithium-containing solution into lithium hydroxide.
Preferably, the dropping speed of the mixed solution into the liquid nitrogen is controlled to be 0.5 to 2 drops/second. In a more preferable mode, the dropping speed of the mixed solution into the liquid nitrogen is controlled to be 1 drop/second. The liquid drops can quickly form rubber balls under the low-temperature action of liquid nitrogen.
As a preferred embodiment, the cross-linking agent includes at least one of glyoxal, triethanolamine, polyethylene glycol, aziridine. These crosslinking agents can chemically crosslink with the reactive groups in the gelling agent.
As a preferred embodiment, the chemical crosslinking reaction process is: and mixing the rubber ball I and the cross-linking agent for reaction for 1-3 min. Through the cross-linking reaction, on one hand, the stability of the rubber ball can be improved, and sodium hydroxide and/or potassium hydroxide are well encapsulated in the microsphere, so that the loss caused by falling off in the subsequent adsorption and precipitation process is prevented; on the other hand, to improve the elasticity and strength of the rubber ball.
Preferably, the time for adsorbing the rubber ball II in the low-concentration lithium-containing solution is 30-120 min. The adsorption and conversion of magnesium ions are facilitated by extending the adsorption time within the preferred time range.
Preferably, the concentration of lithium ions in the low-concentration lithium-containing solution is 10mg/L to 1000 mg/L. The method is suitable for the solution containing lithium ions with lower concentration, can achieve better effects of enriching and recovering the lithium ions, and has strong adaptability.
As a preferred embodiment, the calcination conditions are: calcining for 1-5 h at the temperature of 80-150 ℃. And (3) calcining at low temperature to remove the gel, wherein the gelling agent is decomposed and volatilized or lost under the heating condition, and the remaining precipitate is lithium hydroxide.
As a preferable mode, the gelling agent and sodium hydroxide and/or potassium hydroxide are dissolved in water under heating to form a mixed solution; the heating temperature is 60-90 ℃, and the dissolving time is 5-15 min. Further preferably, the heating temperature is 70-80 ℃, and the dissolving time is 7-10 min. Ensuring that the gelling agent is fully dissolved and mixed with the sodium hydroxide and/or the potassium hydroxide.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the technical scheme of the invention initiatively prepares the gelling agent and the sodium hydroxide and/or the potassium hydroxide into the sodium hydroxide (potassium hydroxide) -containing rubber ball through the working procedures of dissolution, liquid nitrogen condensation, crosslinking and the like, the rubber ball can quickly and efficiently adsorb and enrich lithium ions in a low-concentration lithium-containing solution, the lithium ions are converted into lithium hydroxide precipitates in the rubber ball, and the rubber ball adsorbing the lithium ions can quickly and naturally settle, thereby greatly improving the solid-liquid separation efficiency.
According to the technical scheme, the recovery efficiency of the low-concentration lithium-containing solution by using the rubber ball is high, the recovery rate of lithium is up to more than 93%, lithium hydroxide can be directly prepared by low-temperature calcination after the lithium ions are adsorbed, and the purity of a lithium hydroxide product is more than 95%.
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FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the claims of the present invention is not limited by the following examples.
Example 1
(1) Selecting a certain low-concentration lithium-containing solution of Qinghai, wherein the concentration of lithium ions is 150 mg/L. Gelatin and sodium hydroxide are mixed according to the mass ratio of 2.5: 1, adding the gelatin into warm water at 90 ℃, controlling the mass percentage concentration of the gelatin in the mixed solution to be 5%, adding sodium hydroxide which is 2.5 times of the theoretical amount required by lithium ions in the lithium-containing solution to form lithium hydroxide precipitates, and dissolving for 12min to form a mixed solution I;
(2) dropwise adding the mixed solution I in the step (1) into liquid nitrogen at the speed of 1 drop/second, and quickly forming a rubber ball I under the action of low temperature;
(3) placing the rubber ball I in the step (2) into glyoxal for chemical crosslinking, and after crosslinking for 1min, washing with water to obtain a rubber ball II;
(4) adding the rubber ball II in the step (3) into a lithium-containing solution, and adsorbing for 65min to obtain a rubber ball III adsorbing lithium ions;
(5) and (3) placing the rubber ball III in the step (4) in a muffle furnace, and calcining for 2.5h at the temperature of 90 ℃ to obtain a lithium hydroxide product, wherein the total recovery rate of lithium is 93%, and the purity of the lithium hydroxide product is 95%.
Example 2
(1) Selecting a certain low-concentration lithium-containing solution in Tibet, wherein the concentration of lithium ions is 300 mg/L. Gelatin and sodium hydroxide are mixed according to a mass ratio of 4: 1, adding the gelatin into warm water at 85 ℃, controlling the mass percentage concentration of the gelatin in the mixed solution to be 7%, adding sodium hydroxide which is 2 times of the theoretical amount required by lithium ions in the lithium-containing solution to form lithium hydroxide precipitate, and dissolving for 10min to form a mixed solution I;
(2) dropwise adding the mixed solution I in the step (1) into liquid nitrogen at the speed of 1 drop/second, and quickly forming a rubber ball I under the action of low temperature;
(3) placing the rubber ball I in the step (2) into aziridine for chemical crosslinking, and after crosslinking for 2min, washing with water to obtain a rubber ball II;
(4) adding the rubber ball II in the step (3) into a lithium-containing solution, and adsorbing for 85min to obtain a rubber ball III adsorbing lithium ions;
(5) and (3) placing the rubber ball III in the step (4) in a muffle furnace, and calcining for 3h at the temperature of 100 ℃ to obtain a lithium hydroxide product, wherein the total recovery rate of lithium is 95%, and the purity of the lithium hydroxide product is 96%.
Example 3
(1) Selecting a certain low-concentration lithium-containing solution in Xinjiang, wherein the concentration of lithium ions is 600 mg/L. Mixing glucan gel and sodium hydroxide according to a mass ratio of 5:1, adding into warm water at the temperature of 80 ℃, controlling the mass percentage concentration of the sephadex in the mixed solution to be 8%, adding sodium hydroxide which is 2.5 times of the required theoretical amount of lithium hydroxide precipitate formed by all lithium ions in the lithium-containing solution, and dissolving for 15min to form a mixed solution I;
(2) dropwise adding the mixed solution I in the step (1) into liquid nitrogen at the speed of 1 drop/second, and quickly forming a rubber ball I under the action of low temperature;
(3) placing the rubber ball I in the step (2) into glyoxal for chemical crosslinking, and after crosslinking for 2min, washing with water to obtain a rubber ball II;
(4) adding the rubber ball II in the step (3) into a lithium-containing solution, and adsorbing for 90min to obtain a rubber ball III adsorbing lithium ions;
(5) and (3) placing the rubber ball III in the step (4) in a muffle furnace, and calcining for 2.5h at the temperature of 110 ℃ to obtain a lithium hydroxide product, wherein the total recovery rate of lithium is 94%, and the purity of the lithium hydroxide product is 95%.
Comparative example 1
(1) Selecting a certain low-concentration lithium-containing solution in Tibet, wherein the concentration of lithium ions is 300 mg/L. Gelatin and sodium hydroxide are mixed according to the mass ratio of 5:1, adding the gelatin into warm water at 85 ℃, controlling the mass percentage concentration of the gelatin in the mixed solution to be 30%, adding sodium hydroxide which is 1.5 times of the theoretical amount required by lithium ions in the lithium-containing solution to form lithium hydroxide precipitate, and dissolving for 10min to form a mixed solution I; the mixed solution I has high viscosity and poor solution fluidity, and is difficult to be normally dripped into liquid nitrogen to form the rubber ball I.
Comparative example 2
(1) Selecting a certain low-concentration lithium-containing solution of Qinghai, wherein the concentration of lithium ions is 200 mg/L. Gelatin and sodium hydroxide are mixed according to the mass ratio of 3: 1, adding the gelatin into warm water at the temperature of 80 ℃, controlling the mass percentage concentration of the gelatin in the mixed solution to be 6%, adding sodium hydroxide which is 0.7 times of the theoretical amount required by lithium ions in the lithium-containing solution to form lithium hydroxide precipitate, and dissolving for 12min to form a mixed solution I;
(2) dropwise adding the mixed solution I in the step (1) into liquid nitrogen at the speed of 1 drop/second, and quickly forming a rubber ball I under the action of low temperature;
(3) placing the rubber ball I in the step (2) into glyoxal for chemical crosslinking, and after crosslinking for 2min, washing with water to obtain a rubber ball II;
(4) adding the rubber ball II in the step (3) into a lithium-containing solution, and adsorbing for 80min to obtain a rubber ball III adsorbing lithium ions;
(5) and (3) placing the rubber ball III in the step (4) in a muffle furnace, and calcining for 2.5h at the temperature of 100 ℃ to obtain a lithium hydroxide product, wherein the total recovery rate of lithium is 68%, and the purity of the lithium hydroxide product is 97%.
Claims (8)
1. A method for preparing lithium hydroxide by using a low-concentration lithium-containing solution is characterized by comprising the following steps: the method comprises the following steps:
1) dissolving a gelling agent and sodium hydroxide and/or potassium hydroxide in water to obtain a mixed solution; the gelling agent comprises at least one of gelatin, xanthan gum, dextran gel, polyacrylamide gel and guar gum; the mass percentage concentration of the gelatinizer in the mixed solution is 3-10%;
2) dropwise adding the mixed solution into liquid nitrogen to form a rubber ball I;
3) carrying out chemical crosslinking reaction on the obtained rubber ball I through a crosslinking agent to obtain a rubber ball II;
4) placing the rubber ball II in a low-concentration lithium-containing solution to adsorb and precipitate lithium ions to obtain a rubber ball III;
5) calcining the rubber ball III to obtain a lithium hydroxide product;
2. the method of claim 1, wherein the lithium hydroxide is prepared from a low-concentration lithium-containing solution, and the method comprises the following steps: the mass ratio of the gelling agent to the sodium hydroxide and/or potassium hydroxide is 1: 1-15: 1.
3. The method of claim 1, wherein the lithium hydroxide is prepared from a low-concentration lithium-containing solution, and the method comprises the following steps: the dosage of the sodium hydroxide and/or the potassium hydroxide is 1-5 times of the theoretical molar quantity of the sodium hydroxide and/or the potassium hydroxide required by the lithium ions in the low-concentration lithium-containing solution to be completely converted into the lithium hydroxide.
4. The method of claim 1, wherein the lithium hydroxide is prepared from a low-concentration lithium-containing solution, and the method comprises the following steps: the speed of dripping the mixed solution into liquid nitrogen is controlled to be 0.5-2 drops/second.
5. The method of claim 1, wherein the lithium hydroxide is prepared from a low-concentration lithium-containing solution, and the method comprises the following steps: the cross-linking agent comprises at least one of glyoxal, triethanolamine, polyethylene glycol and aziridine.
6. The method of claim 1, wherein the lithium hydroxide is prepared from a low-concentration lithium-containing solution, and the method comprises the following steps: the chemical crosslinking reaction process comprises the following steps: and mixing the rubber ball I and the cross-linking agent for reaction for 1-3 min.
7. The method of claim 1, wherein the lithium hydroxide is prepared from a low-concentration lithium-containing solution, and the method comprises the following steps: the time for adsorbing the rubber balls II in the low-concentration lithium-containing solution is 30-120 min; the concentration of lithium ions in the low-concentration lithium-containing solution is 10 mg/L-1000 mg/L.
8. The method of claim 1, wherein the lithium hydroxide is prepared from a low-concentration lithium-containing solution, and the method comprises the following steps: the calcining conditions are as follows: calcining for 1-5 h at the temperature of 80-150 ℃.
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